CN104609632B - Zero-discharge treating process for coking wastewater - Google Patents
Zero-discharge treating process for coking wastewater Download PDFInfo
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- CN104609632B CN104609632B CN201510073468.8A CN201510073468A CN104609632B CN 104609632 B CN104609632 B CN 104609632B CN 201510073468 A CN201510073468 A CN 201510073468A CN 104609632 B CN104609632 B CN 104609632B
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- 238000004939 coking Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 37
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- 238000001223 reverse osmosis Methods 0.000 claims abstract description 42
- 238000001704 evaporation Methods 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 26
- 238000005374 membrane filtration Methods 0.000 claims abstract description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
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- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
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Abstract
A kind of zero-discharge treating process for coking wastewater, the step such as including biochemical treatment, activated carbon adsorption, softening crystallization, ultrafiltration membrance filter, reverse osmosis membrane filtration, spray evaporation.Present invention process process is simple, convenient operation and management, automaticity are high, operating cost is relatively low, non-secondary pollution, can effectively administer coking chemical waste water, substantially wastewater zero discharge is realized, thoroughly eliminate Organic substance, ammonia nitrogen and the salt in waste water to grade the destruction to environment, all waste water are carried out high-quality reuse simultaneously.Both full-flow process can be processed as the waste water of newly-built coal chemical enterprise, it is also possible to dock with existing coal chemical enterprise waste water treatment process.
Description
Technical field
The present invention relates to waste water process, particularly to a kind of zero-discharge treating process for coking wastewater.
Background technology
Coking chemical waste water be in coal coke, gas purification and coke chemicals removal process produce containing a large amount of aromatic series
And the waste water of fused ring compound and heterocyclic compound (phenol cyanogen class), have that discharge capacity is big, salt concentration concentration is high, hardness
Higher, Organic substance and the feature such as ammonia nitrogen concentration is high, biodegradability is poor, Organic substance complicated, intractability are big,
Belong to the highly salt containing organic waste water of difficult for biological degradation.
At present, Treatment of Coking Effluent approach mainly includes diluting biochemical process, Chemical treatment method and being directly used in wet
Method quenching etc..Higher containing salinity due to coking chemical waste water itself, must consume a large amount of technique to meet biochemical condition
Water is diluted, additionally heterocycle and the polycyclc aromatic compound such as the phenols in waste water, naphthalene, cyanogen, pyridine, quinoline
All being difficult to biodegradation, therefore dilution biochemical process not only waste water resource, and poor processing effect, water outlet tends not to
Stably reaching standard.Chemical method removes the suspended impurity in waste water and organic contamination by adding a large amount of chemical agents
Thing, the effluent quality of this method is unstable, reagent cost is high, can introduce secondary pollution, adds medicament also simultaneously
The difficulty of follow-up desalting processing can be increased, be phased out maybe working in coordination with other process means at present and use.
It is only then pollutant transfer that coking chemical waste water is directly used in wet quenching, is not effectively addressed；The opposing party
The face coking chemical waste water water yield is typically much higher than supporting wet quenching water, actual and infeasible.
Along with the most harsh to the raising of environmental protection consciousness and relevant environmental regulation and industry access condition of compatriots,
The pattern directly discharged after waste water carries out extensive style process is the most unworkable at coking industry.In recent years, height is sought
Effect, energy-conservation Treatment of Coking Effluent, especially Recycle Technology of Waste Water is just becoming the study hotspot in industry.Due to film
Developing rapidly and wide range of industrial applications of technology, uses MBR film, ultrafilter membrane and reverse osmosis membrane etc. to combine tradition raw
Change, materialization group technology is increasingly becoming Treatment of Coking Effluent and the application trend in reuse field.
Chinese patent CN103112991A discloses a kind of coking wastewater processing system and coking waste water treatment method,
Big single including the process of coking chemical waste water coal tar, coking chemical waste water oxidation and biochemical treatment and coking wastewater deep treatment three
Unit.Wherein coking chemical waste water coal tar processing unit includes oil removal, air supporting and acid out step, mainly in order to remove difference
Granular size and coal tar of different nature；Coking chemical waste water oxidation and biochemical treatment unit include one-level electrocatalytic oxidation
Change, one-level precipitation, anaerobism, anoxia, aerobic, two grades of electrocatalytic oxidations, two-stage precipitation, BAF and
The steps such as membrane biological reaction, main purpose is the Organic substance in treatment of Coking Wastewater；Coking wastewater deep treatment unit
Filter and osmosis filtration including one-level coarse filtration, two grades of coarse filtration, one-level security personnel's filtration, nanofiltration filtration, two grades of security personnel
Etc. step.Use coal tar that this open method can effectively remove in coking chemical waste water, float, Organic substance and
Ammonia nitrogen, the coking chemical waste water COD value processed of final output is relatively low, can reach discharge standard.But this is open
Method has the drawback that (1) complex process, flow process are tediously long, and complex operation, management difficulty are big, actual work
Journey investment makes enterprise be difficult to bear with operating cost is huge；(2) nanofiltration and reverse osmosis in concentration process except receiving
The impact that machine pollutes, is the most usually limited by inorganic factors such as total salinity and hardness, and is not provided with in the method
Corresponding effectively except hard pretreatment measure；(3) the dense water of nanofiltration and reverse osmosis concentrated water described in are all back to front end regulation
Pond, this is infeasible, because this can cause intrasystem total salinity, hardness and undegraded Organic substance in system
Circulation is also enriched with rapidly, ultimately results in nanofiltration and reverse osmosis membrane system owing to osmotic pressure is too high or fouling membrane, fouling are tight
Weigh and stoppage in transit of paralysing；(4) do not account for existing coke-oven plant to have gone into operation the utilization of waste water disposal facility run.
Chinese patent CN103466890A discloses a kind of coking wastewater deep treatment and reclamation set and application thereof
Method, Chinese patent CN102976511A discloses the recoverying and utilizing method of coking chemical waste water film-filter concentration liquid, in
State's patent CN102874990A discloses three embrane method advanced treatment process of coking waste water and equipment thereof, three above
Open method all uses various preprocessing means degradation of organic substances, prevents the organic contamination of film, utilizes embrane method to coking
Waste water carries out degree of depth Treatment for Reuse, reclaims the water resource of a part of high-quality.But there is common problem in them: (1)
Do not account for preventing the pretreatment measure of membranous system fouling, and coking chemical waste water height salinity, high rigidity, membrance concentration,
Filter process will certainly cause fouling and the pollution of film, thus cause the problem such as flux decline, the lost of life；(2)
Do not hand over reverse osmosis or the outlet of nanofiltration this strand of enriching pollutants liquid of dense water or use it for blast-furnace slag cooling, punching
Slag use water, coal yard dust suppression etc..This strand of enriching pollutants liquid contains the salinity of undegradable Organic substance and high concentration
(TDS:10000～20000mg/L), and fouling tendency is clearly, direct discharge can cause most evil bad ring
Border is destroyed, and simple reuse can make the equipment of reuse, pipeline cause corrosion and scaling and damage.
Chinese patent CN101851046A discloses a kind of coking wastewater deep treatment and full reclamation set and answers
By method, the method using biochemistry, oxidation to combine plus membrane separation technique and evaporation carries out the degree of depth to coking chemical waste water
Process and reach zero-emission, being that pollutant each in coking chemical waste water is degraded by one, and by complete for water after process
The new processing method of reuse.But employing the method, can consume a large amount of oxidant, reagent cost is high, evaporation energy consumption is high,
Not about the high rigidity removal measure in coking chemical waste water to prevent reverse osmosis membrane and fouling of evaporator, dirt from blocking up, and not
Consider the coking impact on evaporation of the remaining Organic substance.
Summary of the invention
The purpose of the present invention, in that a kind of zero-discharge treating process for coking wastewater is provided.
The object of the present invention is achieved like this: a kind of zero-discharge treating process for coking wastewater, including biochemical treatment,
Also include following subsequent step:
A, activated carbon adsorption
Waste water after biochemical treatment is imported activated carbon adsorber, the remaining Organic substance in waste water is adsorbed
Removing；
B, softening crystallization
Waste water after the remaining Organic substance of activated carbon adsorber removing is imported and softens crystallizer, add except hard medicine
Agent, removes Ca, Mg hardness of water body；
C, ultrafiltration membrance filter
Waste water after softening crystallization is imported ultrafiltration membrance filter system, carries out solid-liquid separation, solid suspension quilt
Retaining, ultrafiltration permeate enters next step；
D, reverse osmosis membrane filtration
Ultrafiltration permeate is imported reverse osmosis membrane filtration system, and reverse osmosis permeate is as pure water reuse, reverse osmosis concentrated
Water enters next step；
E, spray evaporation
Reverse osmosis concentrated water being imported spray evaporation system be evaporated, condensed fluid is incorporated as pure with reverse osmosis permeate
Water circulation, the solid salt that evaporation obtains as side-product reuse or is sold outward.
Also including active carbon microwave regenerating unit, this active carbon microwave regenerating unit connects activated carbon adsorber；Work as work
After activated carbon adsorption in property charcoal adsorption tower is saturated, it is conducted into active carbon microwave regenerating unit, utilizes microwave energy to make
The Organic substance of activated carbon adsorption discharges from activated carbon capillary, makes activated carbon activity recovery, difficult degradation simultaneously
Larger molecular organics is converted into degradable small organic molecule through microwave action by pyrolytic, is back to after condensation
Biochemical treatment system.
Also including aerating system, this aerating system connects ultrafiltration membrance filter system, it is achieved to ultrafiltration membrance filter system
Intermittent aeration cleans.
Also including sludge condensation and dewatering system, this sludge condensation and dewatering system connect softening crystallizer and ultrafilter membrane
Filtration system, collects and softens the mud that crystallizer and ultrafiltration membrance filter system produce, concentrated after use filter press
Machine, band filter, screw extrusion dewaterer or centrifugal dehydrator are dehydrated, the solid slag discharge after dehydration, clearly
Liquid is transmitted back to ultrafiltration membrance filter system.
Described activated carbon adsorber uses outstanding fluidized bed form, and the specific surface of described activated carbon is 300～1000m2/ gram；
The heating and temperature control of described active carbon microwave regenerating unit is at 150～650 DEG C.
Described softening crystallizer is equipment reaction, clarified separation organically combined, and bottom is reaction zone, and top is
Settling section；Liquid upflow velocity in reaction zone is more than 35mm/s.
Described ultrafiltration membrance filter system uses immersion ultrafiltration, and the aperture of ultrafilter membrane is 0.002～0.1 μm；Ultrafilter membrane
Filtered version use external-compression type filter, filter pressure is 0.01MPaG～0.1MPaG.
Described reverse osmosis membrane filtration system uses first-stage reverse osmosis film or multi-stage reverse osmosis film cascade or multistage reverse osmosis
Film cascade, the salt rejection rate of reverse osmosis membrane is 90%～99.7%；The high-pressure pump of reverse osmosis membrane filtration system uses frequency conversion
Control, can be adjusted according to the pollution condition of influent quality and reverse osmosis membrane.
Described spray evaporation system uses single effect evaporation or multiple-effect evaporation；Evaporation thermal source or power use steam or machinery
Compressor or the hot water of more than 85 DEG C.
Due to the fact that and have employed above technical scheme so that it is compared with prior art, have the following advantages that and special
Point:
1, present invention process process is simple, convenient operation and management, automaticity are high, operating cost is relatively low, nothing
Secondary pollution, can effectively administer coking chemical waste water, substantially realize Zero-discharge coked wastewater, thoroughly eliminates in waste water
Organic substance, ammonia nitrogen and salt grade the destruction to environment, all waste water are carried out high-quality reuse simultaneously.
2, the invention provides the regeneration of perfect pretreatment system, especially activated carbon adsorption and microwave activated carbon can
Removing the Organic substance in water body, the degraded the most treatable larger molecular organics of biochemistry further, softening crystallizer can go
Except the hardness in water body eliminates the fouling factor, solution Organic substance, SS, the hardness etc. of working along both lines is to ultrafilter membrane, anti-
Permeable membrane and the operating fouling of spray evaporation, coking impact, drastically increase bi-membrane method in Treatment of Coking Effluent
With the probability that recovery field realizes industrialization promotion.
3, evaporation uses vacuum spraying evaporation, and making evaporation of water is solid space evaporation by traditional surface evaporation,
Its evaporation intensity is traditional 10～50 times, and evaporation equipment specification can be made to reduce, and can use low-grade 85 DEG C with
On hot water as adding thermal medium, both reduced energy consumption, it is achieved energy-saving and cost-reducing, and can effectively eliminate in evaporation process again
Bubble-related issues, it is ensured that system even running.
The present invention both can process full-flow process as the waste water of newly-built coal chemical enterprise, it is also possible to looks forward to existing coking
Industry waste water treatment process docks.
Accompanying drawing explanation
Fig. 1 is the flow chart of zero-discharge treating process for coking wastewater of the present invention.
Detailed description of the invention
Embodiment 1
Coking chemical waste water after ammonia still process and the oil removal treatment of learning from else's experience is as pending raw water, water yield 100m3/ h, coking
Waste water quality is as shown in table 1:
Table 1
| Project | Unit | Numerical value |
| pH | 9～11 | |
| Colourity | Times | 105 |
| SS | mg/L | 65 |
| NH4 + | mg/L | 274 |
| COD | mg/L | 3880 |
| BOD | mg/L | 1050 |
| Ca2+ | mg/L | 70 |
| TDS | mg/L | 3670 |
| Oils | mg/L | 0.5 |
| TOC | mg/L | 1233 |
Coking chemical waste water first returned sludge with sedimentation tank enters anaerobic reactor in the lump, and its major function is release
Phosphorus, carries out ammonification to partial organic substances simultaneously；The water outlet of anaerobic reactor enters anoxic reacter and carries out denitrogenation processing,
Nitrate nitrogen therein is sent here by aerobic reactor by interior circulation；Waste water after denitrogenation is introduced aerobic reaction
Device, carries out the removal of COD/BOD, nitrification and absorption phosphorus at this, and a part of mixed-liquor return is to anoxic reacter；
Water outlet after aerobic reaction is introduced into sedimentation tank, carries out mud-water separation, and a part for mud is back to anaerobic reactor,
Supernatant enters subsequent processing units as producing water.After above-mentioned biochemical treatment system processes, the COD in waste water
Being greatly lowered with ammonia nitrogen concentration, clearance respectively reaches 90% and 95%, i.e. COD in waste water < 100mg/L,
Ammonia nitrogen < 25mg/L.
Bio-chemical effluent enters activated carbon adsorber, adsorbs de-further to hardly degraded organic substance remaining in waste water
Removing, make the COD < 50mg/L in waste water, < 15mg/L meets subsequent ultrafiltration film, reverse osmosis membrane system enters to ammonia nitrogen
Water is to Organic substance and the requirement of ammonia nitrogen.
After activated carbon adsorption certain time, adsorption capacity is the most saturated, and adsorption efficiency reduces or loses, now will absorption
Saturated activated carbon imports active carbon microwave regenerating unit online.Owing to the saturated activity charcoal containing certain moisture is to inhale
Wave material, the moisture vaporized expanding that when utilizing microwave heating, it is internal will adsorb Organic substance in micropore to be peeled off, blows out,
The larger molecular organics of hardly-biodegradable can be converted into degradable little by the localized hyperthermia that microwave heating produces simultaneously
Molecular organic, consequent a small amount of vaporization and condensation regeneration liquid waste is back to anaerobic reactor circulation biochemical treatment.
Remove organic waste water further through activated carbon adsorber and be introduced into softening crystallizer, add except hard medicine
Agent, utilizes the crystallizer that softens with special construction to remove Ca, Mg hardness in water body, and crystallizer produces in water
Ca2+< 20mg/L, Mg2+< 50mg/L, thoroughly eliminates Ca, Mg fouling tendency, even if making follow-up reverse osmosis membrane
Concentrating 4～5 times does not has fouling dirt to block up risk yet.Crystallizer produces water and certainly flows into submerged ultrafiltration filtration system, passes through
Suction pump will transmit through liquid and is collected in ultrafiltration product water tank, and the solid suspension in waste water is trapped, i.e. at membrance separation
In pond, enrichment concentrates.Ultrafilter membrane uses dead-end filtration form, Water Sproading rate almost 100%.Periodically bottom membrane cisterna
Carrying out spoil disposal, maintaining the solid suspension concentration in membrane cisterna is about 3%.
Needing the pH regulator that ultrafiltration is produced water to 6 before entering reverse osmosis membrane filtration system, ultrafiltration membrane permeate liquid is led to
Crossing pump and squeeze into reverse osmosis membrane filtration system, reverse osmosis membrane permeate, as industrial pure water reuse, produces water water quality such as table 2
Shown in.The producing water ratio of reverse osmosis membrane is 80%, i.e. aquifer yield is 80m3/ h, filter pressure is 2.0～3.5MPa.
Reverse osmosis concentrated water enters vaporizer and processes.
Table 2
| Project | Unit | Numerical value |
| pH | 6～9 | |
| SS | mg/L | ＜ 1 |
| NH4 + | mg/L | 10 |
| COD | mg/L | 10 |
| TDS | mg/L | ＜ 100 |
Enter the reverse osmosis membrane dense water about 20m of spray evaporation system3/ h, spray evaporation uses two effect MVR evaporations.
MVR evaporation is that pressure and temperature is raised, and heat content is therewith through the compression of mechanical compressor by indirect steam
Increasing, the heating chamber being sent to vaporizer uses as adding vapours, makes feed liquid maintain evaporating state, and heats steaming
Vapour itself transfers heat to material itself and is condensed into water.So, indirect steam to be discarded just is filled
The utilization divided, has reclaimed latent heat, has improve again the thermal efficiency.MVR is used to evaporate 1m3Water only consumes about 40 degree
Electricity, operating cost is only and uses the 1/3 of raw steam raising.Meanwhile, use spray evaporation, there is bigger evaporation
Specific surface, evaporation efficiency is greatly improved, and evaporation is caused by the foam that Organic substance remaining in water is formed at evaporation liquid level
Suppression be also eliminated.The about 20m that evaporation obtains3/ h evaporation condensate and the conduct in the lump of reverse osmosis membrane permeate
Recycle-water, the solid salt that evaporation obtains as side-product reuse or is sold outward.
Claims (4)
1. a zero-discharge treating process for coking wastewater, including biochemical treatment, it is characterised in that also include following
Subsequent step:
A, activated carbon adsorption
Waste water after biochemical treatment is imported activated carbon adsorber, the remaining Organic substance in waste water is adsorbed
Removing；
B, softening crystallization
Waste water after the remaining Organic substance of activated carbon adsorber removing is imported and softens crystallizer, add except hard medicine
Agent, removes Ca, Mg hardness of water body；
C, ultrafiltration membrance filter
Waste water after softening crystallization is imported ultrafiltration membrance filter system, carries out solid-liquid separation, solid suspension quilt
Retaining, ultrafiltration permeate enters next step；
D, reverse osmosis membrane filtration
Ultrafiltration permeate is imported reverse osmosis membrane filtration system, and reverse osmosis permeate is as pure water reuse, reverse osmosis concentrated
Water enters next step；
E, spray evaporation
Reverse osmosis concentrated water being imported spray evaporation system be evaporated, condensed fluid is incorporated as pure with reverse osmosis permeate
Water circulation, the solid salt that evaporation obtains as side-product reuse or is sold outward；
Also including active carbon microwave regenerating unit, this active carbon microwave regenerating unit connects activated carbon adsorber；Work as work
After activated carbon adsorption in property charcoal adsorption tower is saturated, it is conducted into active carbon microwave regenerating unit, utilizes microwave energy to make
The Organic substance of activated carbon adsorption discharges from activated carbon capillary, makes activated carbon activity recovery, difficult degradation simultaneously
Larger molecular organics is converted into degradable small organic molecule through microwave action by pyrolytic, is back to after condensation
Biochemical treatment system；
Described softening crystallizer is equipment reaction, clarified separation organically combined, and bottom is reaction zone, and top is
Settling section；Liquid upflow velocity in reaction zone is more than 35mm/s；
Described spray evaporation system uses single effect evaporation or multiple-effect evaporation；
Also including aerating system, this aerating system connects ultrafiltration membrance filter system, it is achieved to ultrafiltration membrance filter system
Intermittent aeration cleans；
Also including sludge condensation and dewatering system, this sludge condensation and dewatering system connect softening crystallizer and ultrafilter membrane
Filtration system, collects and softens the mud that crystallizer and ultrafiltration membrance filter system produce, concentrated after use filter press
Machine, band filter, screw extrusion dewaterer or centrifugal dehydrator are dehydrated, the solid slag discharge after dehydration, clearly
Liquid is transmitted back to ultrafiltration membrance filter system.
Zero-discharge treating process for coking wastewater the most according to claim 1, it is characterised in that: described activity
Charcoal adsorption tower uses outstanding fluidized bed form, and the specific surface of described activated carbon is 300～1000m2/ gram；Described activated carbon is micro-
The heating and temperature control of ripple regenerating unit is at 150～650 DEG C.
Zero-discharge treating process for coking wastewater the most according to claim 1, it is characterised in that: described ultrafiltration
Membrane filtration system uses immersion ultrafiltration, and the aperture of ultrafilter membrane is 0.002～0.1 μm；The filtered version of ultrafilter membrane is adopted
Filtering with external-compression type, filter pressure is 0.01MPaG～0.1MPaG.
Zero-discharge treating process for coking wastewater the most according to claim 1, it is characterised in that: described reverse osmosis
Permeable membrane filtration system uses first-stage reverse osmosis film or multi-stage reverse osmosis film cascade or the series connection of multistage reverse osmosis membrane, reverse osmosis
The salt rejection rate of film is 90%～99.7%；The high-pressure pump of reverse osmosis membrane filtration system uses VFC, according to water inlet
The pollution condition of water quality and reverse osmosis membrane is adjusted.
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| CN106336066B (en) * | 2015-07-08 | 2020-04-24 | 天津三环乐喜新材料有限公司 | Zero discharge system and method for neodymium iron boron permanent magnet material wastewater |
| CN108623085B (en) * | 2017-03-18 | 2022-05-31 | 深圳市深水生态环境技术有限公司 | Advanced treatment method for high-nitrogen organic wastewater membrane filtration concentrate |
| CN110194500A (en) * | 2018-02-24 | 2019-09-03 | 宝武炭材料科技有限公司 | A kind of system and method using the continuous absorption regeneration processing coking wastewater of active carbon |
| CN108928984B (en) * | 2018-08-08 | 2021-07-20 | 鞍钢股份有限公司 | Method for realizing zero emission of reverse osmosis strong brine in iron and steel enterprises |
| CN109665667A (en) * | 2019-01-07 | 2019-04-23 | 郑州大学综合设计研究院有限公司 | A kind of nylon66 fiber cord fabric wastewater deep treatment process |
| CN111606496B (en) * | 2020-04-28 | 2022-11-25 | 郝东珍 | Coking wastewater treatment device and method |
| CN111517503A (en) * | 2020-05-15 | 2020-08-11 | 江苏阿尔法环保科技有限公司 | COD digestion device and technology in organic wastewater |
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